Cakbocyclic monocarboxyijc acid



Patented Nov. 17, 1953 CARBOCYCLIC MONOCARBOXYLIC ACID SALTS OFGLYOXALIDINES George W. Luvisi, Chicago, 111., assignor to NationalAluminate Corporation, Chicago, 111., a corporation of Delaware NoDrawing. Application September 26, 1950, Serial No. 186,929

9 Claims.

1 This invention relates to new compounds, more particularly tocompounds having the general formula where X is the negative radical ofa carbocyclic monocarboxy acid, R is a higher aliphatic hydrocarbonradical containing at least 11, preferably 1'7 carbon atoms in anacyclic chain, R is hydrogen or a lower aliphatic group containing notmore than 6 carbon atoms, Y i hydrogen or a lower aliphatic groupcontaining not more than 6 carbon atoms, and Z is hydrogen or a loweralkyl group containing not more than six carbon atoms. These compoundsmay also be described generally as carbocyclic monocarboxy acid salts ofglyoxalidines.

These carbocyclic monocarboxy acid salts of glyoxalidines are viscousliquids or soft greases which are characterized by being soluble ordispersible in water. They are easily prepared by mixing the carbocycliccarboxy acid with the glyoxalidine in equimolecular proportions in thecold or by warming the two together at temperatures up to 100 degrees C.for to 15 minutes.

As examples of carboxy acids that may be used to prepare these saltsthere may be mentioned:

benzoic acid, 4-chlorobenzoic acid, 2,4-dichlorobenzoic acid, salicylicacid, cinnamic acid, 3,5- dinitrobenzoic acid, 2-nitrobenzoic acid,3-nitrobenzoic acid, ortho cresotinic acid, anthranilic acid,phenylacetic acid, Z-chlorobenzoic acid, 4-chlorobenz0ic acid,phenoxyacetic, 2,4-dichlorophenoxyacetic acid,2,4,5-trichlorophenoxyacetic acid, pentachlorophenoxyacetic acid,naphthenic acids and 2,4-dichlorobenzoic acid.

Examples of glyoxalidines that may be reacted with any of the foregoingacids in preparing these salts are: l-(2-aminoethyD-2 -heptadecenylglyoxalidine, 1-(2 -hydroxyethyl)-2- heptadecenyl glyoxalidine,4-methyl-2-heptadecenyl glyoxalidine, 1 [2 -(2 aminoethyl) aminoethyl]-2-heptadecenyl glyoxalidine, 1-( 2- aminoethyD-2-undecyl glyoxalidine,1-(2-hydroxyethyD-2-undecyl glyoxalidine, 4-methy1- 2-undecylglyoxalidine, 1 -[2 -(2 aminoethyl) aminoethyl] 2 undecyl glyoxalidine,1 (2 aminoethyl)-2-tridecyl glyoxalidine, 1-(2-hydroxyethyD-2-tridecylglyoxalidine, 4-methyl-2- tridecyl glyoxalidine,1-[2-(2-aminoethyll-ami- 2 noethyll-Z-tridecyl glyoxalidine,1-(2-aminoethyl) -2-pentadecyl glyoxalidine, 1-(2-hydroxyethyl)-2-pentadecyl glyoxalidine, 4-methyl-2- pentadecyl glyoxalidine and1-[2-(2-aminoethyl) -aminoethyll 2-pentadecyl glyoxalidine.

The following is a table containing some of the properties of some ofthe glyoxalidine salts that have been prepared in accordance with theinvention.

The naphthenic acid which has been designated 235 XX Socony Vacuum is afully refined naphthenic acid having a neutralization equivalent of 235.

The solubility test of the glyoxalidine salt in water was conducted byadding one drop of the salt to 10 ml. of Water and agitating andobserving the resulting solution.

The solubility of the glyoxalidine salt in oil was determined by addinone drop of the salt to 10 ml. of an aromatic oil such as thecatalytically cracked product marketed by Shell Oil Company under thetrade name of Shells medium aromatic oil with a boiling range of 430degrees F. to 620 degrees F. and a flash point of 225 degrees F.(Cleveland open cup).

These glyoxalidine salts have shown themselves to be very excellentemulsifying agents for aromatic oils in water. Emulsifying tests wereconducted as follows: One half gram of the slyoxalidine salt wasdissolved in grams of the Shell medium aromatic oil described above. Tothis 450 m1. of water was added with agitation. The stability of theresulting emulsion Was judged by the amount of time required for the oilto start to come out of solution. In some cases no separation of oiloccurred, but a cream layer of emulsion rich in oil was noticed to floatto the top. The time was noted when this separation could be noticed.The various salts of 2- heptadecenyl-4-methyl glyoxalidine and 1-[2- (2aminoethyl) aminoethyl] 2 heptadecenyl glyoxalidineszgere tested at 2%concentration in the oil. Control tests using aliphatic carboxylic acidsalts of glyoxalidines such as the acetic acid and oleic acid salts ofl-(2-hydroxyethyl)- Z-heptadecenyl glyoxalidine were inefiective informing emulsions of this oil even when used at the concentration of 5%in the aromatic oil.

The salts of this invention are outstanding emulsifying agents. Whereasrelatively large amounts (over 5% and up to 25%) of the otheremulsifying agents such as, polyoxyalkylene esters and ethers, petroleumsulphonates, alkyl aryl sulphonates, alkyl sulphates are required toemulsify Shell medium aromatic oil in water,

1% or even less of the glyoxalidine salts of this invention are requiredto give emulsions stable for long periods.

decenyl glyoxalidine salicylate gave an emulsion which was stable forone hour when mixed with 900 ml. of water. When 5.0 grams of theSolubility Reactants Weight Description Solubility in water in aroratiomatic oil 1 (2 hydroxyethyl) 2 e heptadec- 3. 5

enyl glyoxalidine. Homogeneous viscous liquid Cloudy solution; veryviscous; Soluble. 2,4-diclilorophenoxy acetic acid 2. 2 foams copiously.1 (2 hydroxyethyl) 2 heptadec- 3. 5

enyl glyoxalidine. .-do Slightly cloudy; foams copi- Do. Salicylicacid 1. 38 ously; very viscous. 1 (2 hydroxyethyl) 2 heptadec- 3. 5

cnyl glyoxalidine do Clear solution; foams copi- Do. Benzoic acid l. 22ously; viscous. 2 heptadceenyl 4 3. 2

dine. Homogeneous brown viscous liquid. Milky solution; fairly heavy Do.2,4-diehlorophenoxy acetic acid 2. 2 foam. ifgffig ggfi glyoxan g}Homogeneous yellow viscous liquid. Clear gelatinous solution; Do. 1 2 2aminoethyl) am oethylla. as heavy 2-lieptadeccnyl-glyoxalidine.Homogeneous amber viscous liquid. Clear solution; very heavy Insoluble.2,4-dichloroplienoxy acetic acid 2. 2 foam. 1 ggg i igfig g 93Homogeneous deep yellow viscous Clear gelatinous solution; Do. salicylicacid L 38 liquid. very heavy foam. figggg g ff glyoxahdme' Clear brownviscous liquid Disperses in water; some Soluble.

081]". ll ggfig gfigi gg 4'methy1 oxandme' 3 Clear amber viscous liquidTurbid solution; fairly heavy Insoluble.l-[2-(2-aminoethyl)-aminoethyl1-2- 3.93 foam heptadecenyl glyoxalidinc.Cloudy amber tally-like liquid Clear solution; very heavy Do.2,i-dichloro-phenoxyacetic acid 4. 4 foam.l-[2-aminoethyl)-arninocthyl]-2-hepta- 3. 93

dccenyl glyoxalidine. i Clear s lution; extremely D0. Salicylic acid 2.76 heavy foam. l-(2-hydroxyethyl)-2-heptadccenyl 3.

glyoxalid e. Viscous liquid Clear solution; some foam Soluble.Phcnylacetic acid 1. 36 l-(2-hydroxyethyl)-2-heptadecenyl 3. 5

glyoxalidine. Resinous-like paste Hazy solution; some foani Do. Betahydroxy naphthoic acid 1. 88 l-(2-hydroxyethyl)-2-heptadecenyl 3. 5

glyoxalidine. Viscous liquid Hazy solution; some foam; Do. Orthocresotinic acid 1. 52 slightly viscous.l-(2-hydroxyethyl)-2-heptadecenyl 3. 5

glyoxalidine. Tan opaque viscous liquid Hazy solution; some foam S l i gh t 1y 2,4,5-trichloro-phenoxyacetic acid 2. 55 azysol-(2-hydroxyethyl)-2-heptadecenyl 3. 5 lution.

glyoxalidine. Brown clear viscous liquid Milky solution; fair amountClear solu- Pentacblorophenoxy-acetic acid 3. 23 of foam; slightlyviscous. 0nl-(2-hydroi yethyl)-2-heptadecenyl 3. 5

glyoxalidine. Resinous paste Clear solution; lots of foam; Soluble.Anthranilic acid 1. 37 very viscous. 1-(2-hydroxyethyl)-2-heptadecenyl3. 5

glyoxalidine. Viscous oil Clear solution; fair amount of Do. ;2,4dlchlorobenzoic acid 1. 91 foam; extremely viscous.l-(2-hydroxyethyl)-2-heptadecenyl 3. 5

glyoxalidincs. Res ious-like paste Clear solution; some foam Insoluble.Para aminophenyl acetic acid l. 51 l-(2-hydroxyethyl)-2-heptadecenyl 3.5

glyoxalidine. Res ous Solid Slightly soluble; lots of foam D0. Gallicacid 1.7 l-(2-hydroxyethyl) -2-hep ta deccnyl glyoxalidine 3. 5Homogeneous viscous liquid Clear solution; slightly vis- Soluble.3,5-dinitrobenzoic acid 2. 12 cons; lots of foam. l-(2-hydroxyethyl)-2-hep tadecenyl glyoxalidine 3. 5 Viscous Oil Hazy solution; quiteviscous; Do. 2,5-dichlorosalicylic acid 2.07 lots of foam.l-(z-hydroxyethyl) -2-heptadecenyl glyoxalidine 3. 5 -d0 Clear solution;viscous; some Do. Ortho chlorobenzoic acid 1. 57 foam.l-(Z-hydroxyethyl) -2-hepta decenyl glyoxalidine 3. 5 Waxy pas e Hazysolution; viscous; some Do. Para chlorobenzoic acid 1. 57 foam.l-(2hydroxyethyl) -2-hep tadecenyl glyoxalidine 3. 5 Taffy-like viscousoil Clear solution; lots of foam- Disperses Para-hydroxyphenylglycine 1. 67 in l-(2-hydroxyethyl) -2-heptadecenyl alid' 3. 5 oftgrease Hazy solution; very viscous; Soluble.

1. 48 little foam. l-(2-hydroxyethyl) glyoxalidine 3. 5 Wax-like solidClear solution; lots of foam.. Disperses Hippuric acid 1. 79 in oil-(2-liydrpxyethyl) ggmfig iaa'z g' i' 2 5 V cous O l Hazy solution;quite a bit of Soluble. 2 1y ii i'i' "'iii'i'i ""121 g5 foam.

epta 9 y g yoxa 1 Light brown viscous liquid..- Clear solution;extremely vis- Do Cinnamic acid 43 cons; some {0mm glyoxalidine stearatesalt was used the emulsion broke in 10 minutes. One gram of the1-(2-hydroxyethyl) -2-heptadeceny1 glyoxalidine cinnamate saltsubstituted for the salicylate salt gave an emulsion that was stable for72 minutes. The acetate salt even with up to 5 grams gave an emulsionthat was stable for less than 2 minutes.

Example II Ten grams of Chlordane was dissolved in 89 grams of keroseneand 1 gram of the glyoxalidine Very stable emulsions of insecticidessuch as Chlordane, DDT, and Methoxychlor can be made using theseglyoxalidine salts.

The emulsifying properties of these new compounds will be furtherillustrated by the following examples.

Earample I Twenty (20) grams of Methoxychlor dissolved in 79.5 grams ofShell medium aromatic oil containing 0.5 gram of 1-(2-hydroxyethyl)-2-hepta- 75 salicylate salt described above was added. When 10 ml. ofthis mixture was added to 90 ml. of water, the resulting emulsion wasstable about 19 minutes. When prepared with 1 gram of the stearate saltof the same glyoxalidine the Chlordane emulsion broke in minutes. Four(4) grams of the stearate salt gave an emulsion that was stable about 11minutes.

Example III Five (5) grams of DDT was dissolved in 93 grams of Shellmedium aromatic oil and 2 grams of the l-(z-hydroxyethyl)-2-heptadecenylglyoxalidine benzoate described above was added. Ten milliliters of theabove oil was mixed with 90 m1. of water. The resulting emulsion wasstable about fifteen minutes. Under the same conditions 4 grams of thestearate salt of the same glyoxalidine gave an emulsion that was stableabout 6 minutes.

In addition to their ability to emulsify oils in water theseglyoxalidine salts show other very interesting properties. Dilute (1%)aqueous solutions are extremely viscous such as in the case of the2,4-dichlorophenoxyacetic acid, salicyclic acid, anthranilic acid,2,4-dichlorobenzoic acid, orthochlorobenzoic acid, para-chlorobenzoicacid, and cinnamic acid salts of 1-(2-hydroxyethyl) -2-heptadecenylglyoxalidine. Where emulsifying agents and thickening agents are neededin the same composition these compounds are very useful. The substitutedglyoxalidines themselves have the ability to thicken water olutions butthe herein described carbocyclic carboxy acid salts are markedlysuperior in this respect.

The term carbocyclic monocarboxy acid as used herein is intended tocover any monocarboxylic acid containing a carbocyclic ring. The carboxygroup may be linked directly to a carbon atom of the carbocyclic ring ormay be connected to a side alkyl or alkylene group.

The invention is hereby claimed as follows:

1. A compound having the following general formula Where X is thenegative radical of a carbocyclic monocarboxy acid from the groupconsisting of monoand di-carbocyclic acids in which the carbocyclicstructure is from the group consisting of 5-membered and G-memberedcarbon rings, R is a higher aliphatic hydrocarbon radical containing atleast 11 carbon atoms, R and Y are from the group consisting of hydrogenand lower aliphatic groups containing not more than 6 carbon atoms and Zis from the group consisting of hydrogen and lower alkyl groupscontaining not more than 6 carbon atoms.

2. Carbocyclic monocarboxy acid addition salts of 2-heptadecenylglyoxalidines from the group consisting of the monoand dicarbocyclicmonocarboxylic acid addition salts of 2-heptaclecenyl glyoxalidineswherein the carbocyclic structures consist of fi-membered rings.

3. The 2,4-dichlorophenoxyacetic acid addition salt of1-(2-hydroxyethyl)-2-heptacleceny1 glyoxalidine.

4. The salicyclic acid addition salt of 1-(2-hydroxyethyl)-2-heptadecenyl glyoxalidine.

5. The cinnamic acid salt of l-(2-hydroxyethyl) -2-heptadecenylglyoxalidine.

6. The benzoic acid salt of 1-(2-hydroxyethyl) -2-heptadecenylglyoxalidine.

7. The anthranilic acid salt of 1-(2-hydroxyethyl) -2-heptadecenylglyoxalidine.

8. The carbocyclic monocarboxy acid addition salts of glyoxalidinessubstituted in the 2 position with a higher aliphatic acyclichydrocarbon group containing 11 to 17 carbon atoms wherein themonocarboxy acid salt-forming group is derived from an acid from thegroup consisting of 2,4-dichlorophenoxyacetic acid, salicylic acid,2,4-dichlorobenzoic acid, 3,5-dinitrobenzoic acid, 4-chlorobenzoic acidand cinnamic acid.

9. The carbocyclic monocarboxy acid addition salts of 2-heptadecenylglyoxalidines wherein the monocarboxy salt-forming group is derived froman acid from the group consisting of 2,4- dichlorophenoxyacetic acid,salicylic acid, 2,4- dichlorobenzoic acid, 3,5-dinitrobenzoic acid, 4-chlorobenzoic acid and cinnamic acid.

GEORGE W. LUVISI.

References Cited in the file of this patent UNITED STATES PATENTS NumberName Date 2,267,965 Wilson Dec. 30, 1941 2,268,273 Wilkes Dec. 30, 19412,374,354 Kaplan Apr. 24, 1945

1. A COMPOUND HAVING THE FOLLOWING GENERAL FORMULA